HUT73199A - Polymer bound ligands, process for production thereof, polymer bound metallocenes, catalyst systems and polymerization process - Google Patents

Description

The present invention relates to polymer-linked ligands, polymer-linked metallocenes, catalyst systems and processes for their preparation, and to the use of such catalyst systems in the polymerization of olefins.

Metallocene catalysts are used in homogenous solution polymerization. Since such homogeneous catalysts are soluble in the polymerization medium, it is generally observed that the polymer formed is of low bulk density.

Attempts to use soluble metallocene catalysts in slurry or particle-forming polymerization have so far been unsuccessful. It has been found that when the particle-forming polymerization is carried out in the presence of a soluble metallocene catalyst, a large amount of polymeric material is formed on the surface of the polymerization reactor. This deposition adversely affects the heat transfer and results in the reactor being cleaned from time to time, even if not continuously.

In order to overcome these disadvantages, it is necessary to develop economical solid metallocene catalysts which do not cause deposition in the reactors during the polymerization processes.

It is an object of the present invention to provide solid polymer-linked ligands for use in the preparation of heterogeneous metallocene catalysts.

Another object of the present invention is to provide an economical process for the preparation of solid polymer-linked ligands for use in the production of metallocene catalysts.

Another object of the present invention was to provide a solid polymer-bonded metallocene that can be used in the polymerization of olefins so that no significant reactor impurity is formed in the particle-forming polymerization process.

It was also our object to develop an efficient and economical process for the preparation of polymer-linked metallocene catalysts.

It is also an object of the present invention to provide a polymerization process, in particular a particle-forming polymerization process, in which there is no deposit on the wall of the polymerization reactor.

Accordingly, the present invention relates to polymer-linked ligands QM (R) _m and methods for their preparation. In the formula Q is polystyrene, M is Si, C, Ge, Sn, P or N and each R is independently a hydrocarbon group, provided that at least one R is a cyclopentadienyl-type and when M is C , at least two R groups are cyclopentadienyl-type, as defined below, and m is 2 or 3. In the process of the present invention, these compounds are prepared by treating a metallized polystyrene and an organic halide compound wherein the polystyrene is an alkali metal. and wherein the organic halide compound is represented by the formula XM (R) _m wherein X is a halide. The present invention further relates to metallocene linked to a polymer of the formula QM (R) _m ZY _n wherein Z is a transition metal, Y is a halide, methyl, hydrogen or cyclopentadienyl type and n is 2 or 3. The invention further relates to a process as described above. for the preparation of polymer-linked metallocenes, the process comprising reacting the polymer-linked ligand with an alkali metal compound and reacting the resulting metallized polymer-bound ligand with a transition metal halide of formula ZY ₄ . In addition, the present invention provides a catalyst system comprising a polymer-linked metallocene and an organic aluminoxane compound; a process for preparing these catalyst systems; and a polymerization process using the catalyst system.

More particularly, QM (R) _{m of} the present invention has the formula: Q is polystyrene, M is Si, C, Ge, Sn, P or N and each R is an independent hydrocarbon group, provided that at least one is a hydrocarbon group. R is a cyclopentadienyl-type group and when M is C, at least two R groups are a cyclopentadienyl-type group and m is 2 or 3. According to the process of the present invention, these compounds are prepared by an organic halide compound wherein the polystyrene is metallised with an alkali metal and wherein the organic halide compound has the formula XM (R) _m wherein X is halide and M, R and m are as defined above.

By cyclopentadienyl-type is meant a group containing a cyclopentadienyl-type group and includes cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl and substituted fluorenyl. The substituents may be C 1 -C 12 hydrocarbon groups, C 1 -C 12 alkoxy groups or halides. Preferably the substituents are C 1 -C 10, more preferably C 1 -C 6 alkyl. Exemplary substituents include methyl, ethyl, propyl, butyl, tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl. , dodecyl, 2-ethylhexyl, pentenyl, butenyl, phenyl, chloride, bromide and iodide.

The term polystyrene, as used herein, includes polystyrene, cross-linked polystyrene, polystyrene derivatives such as methylated polystyrene, polystyryl cyclopentadiene and (methylated polystyryl) cyclopentadiene, and functionalized polystyrene such as halogenated polystyrene, able.

Polystyrene is commercially available and can be prepared by any process known in the art. An example of a general preparation of polystyrene is the reaction of styrene and divinylbenzene under polymerization conditions. The polymerization conditions can vary over a wide range. Generally, the polymerization is carried out at a temperature of about 20 ° C to about 150 ° C.

Metallized polystyrene may be prepared by any of the methods known in the art. In such a process, the polystyrene is reacted with an alkali metal compound. Alkali metal compounds suitable for the production of metallized polystyrene are represented by the general formula AR ', wherein A is an alkali metal which may be lithium, sodium and potassium and R' is a hydrocarbon group having from 1 to 12 alkyl, cycloalkyl and aryl groups. may. Preferably R is C 1-10 alkyl. The reaction preferably uses lithium (C 1 -C 8) alkyl compounds. Preferred lithium alkyl compounds include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, pentyllithium, and hexyllithium. Excellent results have been obtained when n-butyllithium is used, and the use of this compound is particularly advantageous. The conditions for polystyrene metallization can vary over a wide range. In general, the reaction is carried out at a temperature of about 0 ° C to about 100 ° C. In the production of metallized polystyrene, the alkali metal compound is generally used in an amount of about 0.1 to 50 moles, preferably about 0.2 to 25 moles, and most preferably about 0.5 to 20 moles, per polystyrene.

Alternatively, the metallized polystyrene may be prepared by reacting an alkali metal compound as described above with halogenated polystyrene. In the general method for the preparation of halogenated polystyrene, the polystyrene is reacted with Br ₂ and FeCl ₃ in chloroform as described in J. Org. Chem., Vol. 41, No. 24, pages 3877-3882 (1976). The conditions of this procedure may vary over a wide range. In general, the reaction is carried out at a temperature of about 0 ° C to about 100 ° C. The amount of Br ₂ is generally from about 0.1 to about 50 moles of Br ₂ / kg of polystyrene, preferably from about 0.2 to about 25 moles of Br ₂ / kg of polystyrene, and most preferably from about 0.5 to about 20 moles of Br ₂ / kg of polystyrene. The halogenated polystyrene is then reacted with an alkali metal compound. The amount of alkali metal compound is about 0.1 to 50 moles, preferably about 0.2 to 25 moles, and more preferably about 0.5 to 20 moles, per kg of halogenated polystyrene.

Another possible method for producing metallized polystyrene is by reacting chloromethylated polystyrene with a metallised cyclopentadienyl-type compound. Chloromethylated polystyrene may be prepared by reacting polystyrene with (chloromethyl) alkyl ether wherein the alkyl group contains from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms. The metallised cyclopentadienyl-type compound is an alkali metal salt. The metallized cyclopentadienyl-type compound contains a cyclopentadienyl-type group, which includes the cyclopentadienyl, substituted cyclopentadienyl, indenyl and substituted indenyl groups described above. Suitable metallised cyclopentadienyl-type compounds are commercially available, for example, in the form of sodium cyclopentadiene or sodium indene. Metallized cyclopentadienyl-type compounds can be prepared by any of the methods known in the art. Generally, the cyclopentadienyl-type compound is reacted with an alkali metal such as sodium or an alkali metal compound such as that described above for the preparation of metallized polystyrene according to the procedure described in J. Am. Chem. Soc., 73, 5135-7. Page 5138. For example, (C 1 -C 8 alkyl) lithium and (C 1 -C 8 alkyl) sodium compounds are particularly preferred in the above reaction. The reaction conditions for the preparation of the metalated cyclopentadienyl-type compound can vary widely depending on the reaction partners employed. Generally, the reaction is carried out at a temperature of about 0-200 ° C. The metallised cyclopentadienyl-type compound is then reacted with chloromethylated polystyrene to produce a cyclopentadienyl-type polystyrene, such as (methylated polystyryl) cyclopentadiene or (methylated polystyryl) indene. The alkali metal compound described above is then reacted with cyclopentadienyl-type polystyrene to produce metallized polystyrene. A general procedure is described in J. Am. Chem. Soc., 95, 2373-2375. (1973) and J. Am. Chem. Soc., 97: 8, 2128-2132. (April 16, 1975). The reaction uses (chloromethyl) alkyl ether in an amount of about 0.1 to 50 mol, preferably about 0.2 to 25 mol, and more preferably about 0.5 to 20 mol, per kg of polystyrene. In the reaction, the metalized cyclopentadienyl-type compound is used in an amount of about 0.1 to 50 mol, preferably about 0.2 to 25 mol, more preferably about 0.5 to 20 mol, per kg of chloromethylated polystyrene. In the reaction, the alkali metal compound is used in an amount of about 0.1 to 50 mol, preferably about 0.2 to 25 mol, and more preferably about 0.5 to 20 mol, per kg of polystyrene. In the preparation of metallized polystyrene, the reaction temperature is generally from about 0 ° C to about 100 ° C.

The metallized polystyrene is then reacted with an organic halide compound. The organic halide compound is represented by the formula XM (R) _m wherein X is halide, M is Si, C, Ge, Sn, P or N and each R is a hydrocarbon having from 1 to 36 carbon atoms, preferably 1 to 36 carbon atoms. It may be a C 24 alkyl, cycloalkyl, aryl or cyclopentadienyl group, provided that at least one R 1 -. .

is a cyclopentadienyl-type group, and when M is C, at least two R substituents are a cyclopentadienyl-type group and m is 2 or 3. Chlorosilanes are preferred as the organic halide compound. Examples of suitable organic halide compounds include chlorocyclopentadienyldiphenylsilane, chlorodicyclopentadienylmethylsilane, chlorocyclopentadienyl- (9-fluorenyl) methylsilane, chlorodifluorenylmethylsilane, chloro- cyclopentadienylmethylphenylsilane, chloro- (1-indenyl) (9-fluorenyl) phenylsilane, chlorodiphenyl (9-fluorenyl) silane, chloro- (9-fluorenyl) methylphenyl- silane, chlorodimethyl- (1-indenyl) silane, chlorodiodenylmethylsilane, chlorocyclopentadienyl diphenyl methane, chlorodicyclopentadienyl methyl methane, chlorocyclopentadienyl (9-fluorenyl) methyl- methane, chlorodifluorenylmethylmethane, chlorocyclopentadienylmethylphenylmethane, chloro (1-indenyl) (9-fluorenyl) phenylmethane, chlorodiphenyl (9-fluorenyl) methane, chloro (9-fluorenyl) methylphenylmethane, chlorodimethyl (1-indenyl) methane and chlorodinedenylmethylmethane. Chlorodiphenyl (9-fluorenyl) silane and chlorocyclopentadienyl (9-fluorenyl) methyl silane are preferred as organic halide compounds.

The organic halide compounds may be prepared by methods known in the art. One such method is described in Sommer et al., J. Am. Chem. Soc., 73, 5135-5138, under the title "Silylindenes and Silylindans". The process involves reacting organic halosilanes, such as dimethyldichlorosilane, with metallised cyclopentadienyl-type compounds such as 1-indenyl sodium or 1-indenyl lithium. Typical examples include the reaction of dichlorodiphenylsilane with fluorenyl lithium or the reaction of 9-fluorenylmethyldichlorosilane with cyclopentadienyl sodium and the reaction of methyl trichlorosilane with two equivalents of fluorenyl lithium. Metallized cyclopentadienyl-type compounds can be prepared as described above. The reaction conditions used for the preparation of the organic halide compounds may vary widely depending on the reactants used.

In the reaction between the organic halide compound and the metallized polystyrene, the organic halide compound is generally used in an amount of from about 0.1 to about 50 moles, preferably from about 0.2 to about 25 moles, and more preferably from about 0.5 to about 20 moles. The metallized polystyrene is reacted with the organic halide compound at a temperature of about 0 ° C to about 100 ° C.

Examples of polymer-linked ligands include the following: cyclopentadienyldiphenyl polystyrylsilane, dicyclopentadienylmethyl polystyrylsilane, cyclopentadienyl (9-fluorenyl) methyl polystyrylsilane, cyclopentadienyl- (9-fluorenyl) methyl polystyrylmethylsilane, difluorenylmethyl-polystyrylsilane, cyclopentadienylmethyl-phenyl-polystyrylsilane, (1-indenyl) - (9-fluorenyl) -phenyl-polystyrylsilane, diphenyl- (9-fluorenyl) - polystyrylsilane, diphenyl (9-fluorenyl) (polystyrylmethyl) silane, diphenyl (9-fluorenyl) (polystyrylcyclopentadienyl) silane, (9-fluorenyl) methylphenyl polystyrylsilane, dimethyl- (1-indenyl) -polystyrylsilane, (1-indenyl) -methyl-phenyl-polystyrylsilane, methyl-diindenyl-polystyryl-silane, cyclopentadienyl-diphenyl-polystyrylmethane, dicyclopentadienyl-methyl-polystyryl-methane, cyclopentadienyl- -fluorenyl) -methyl-polystyrylmethane, cyclopentadienyl- (9-fluorenyl) -methyl- (polystyrylmethyl) -methane, difluorenyl-methyl -polystyryl methane, cyclopentadienylmethylphenyl polystyryl methane, (1-indenyl) (9-fluorenyl) phenyl polystyryl methane, diphenyl (9-fluorenyl) polystyryl methane, diphenyl (9-fluorenyl) - (polystyryl-cyclopentadienyl) -methane, (9-fluorenyl) -methyl-phenyl-polystyryl-methane, dimethyl- (1-indenyl) -polystyryl-methane, methyl- (1-indenyl) -polystyryl-methane and diindenyl-methyl polystyryl phenyl-methane. The following compounds are preferred as polymer-linked ligands: diphenyl (9-fluorenyl) (polystyrylcyclopentadienyl)

.........

Ian, cyclopentadienyl (9-fluorenyl) methyl polystyrylsilane, and diphenyl (9-fluorenyl) polystyrylsilane.

The metallocenes linked to the polymer of formula QM (R) _m ZY _n can be prepared by providing a metallized polymer-bound ligand with a metal halide wherein Z is a transition metal which may be Zr, Hf, Ti or V and wherein each Y is each independently is a halide, methyl, hydrogen, or C 5 -C 36 cyclopentadienyl-type, with the proviso that at least three Y substituents are halide. Cyclopentadienyl-type groups may be those described above for the organic halide compound. Metallized, polymer-linked ligands can be prepared by reacting the polymer-linked ligand with an alkali metal compound. The reaction conditions and alkali metal compounds used to prepare the metallized polymer-linked ligand are the same as those described above for the preparation of the metallized polystyrene and the reaction temperature is about 0-100 ° C.

The metal halides are represented by the formula ZY ₄ , wherein Z and Y are as defined above. Suitable metal halides, the following compounds are TiCl _4, ZrCl _4, HfCl _4, VC1 _4, TIBRO _4, ZrBr _4, HFBR _4, VBr _4, Til _4, Zrl _4, Hfl _4, IP _4, cyclopentadienyl zirconium trichloride, cyclopentadienyl titanium trichloride; cyclopentadienyl hafnium trichloride; cyclopentadienyl vanadium trichloride; indenyl zirconium trichloride and indenyl titanium trichloride. Zirconium-containing and titanium-containing metal halides are preferred. Zirconium-containing metal halides are more preferred and zirconium tetrachloride and cyclopentadienyl zirconium trichloride are most preferred.

• ·

- · · · ♦ ·

The amount of metal halide is about 0.1 to 50 moles, preferably about 0.2 to 25 moles, and most preferably about 0.5 to 20 moles, per kg of polymer-bound ligand. The metallized polymer-linked ligand is generally reacted with the metal halide at a temperature of about 0 ° C to about 100 ° C.

Examples of polymer-linked metallocenes include diphenyl- (9-fluorenyl) (polystyrylcyclopentadienyl) silane zirconium dichloride, diphenyl- (9-fluorenyl) polystyrylmethylsilane cyclopentadienyl zirconium. dichloride, diphenyl- (9-fluorenyl) -polystyrylsilane-cyclopentadienyl-zirconium dichloride, cyclopentadienyl-diphenyl-polystyryl-silicon-cyclopentadienyl-zirconium dichloride, dicyclopentadienyl-methyl-polystyrene-dicyclo-dichloride, 9-fluorenyl) methyl polystyrylsilane zirconium dichloride, cyclopentadienyl (9-fluorenyl) methyl (polystyrylmethyl) silane zirconium dichloride, difluorenylmethyl polystyrylsilane zirconium dichloride, cyclopentadiene -methylphenyl-polystyrylsilane-indenyl-zirconium dichloride, (1-indenyl) - (9-fluorenyl) -phenyl-polystyrylsilane-zirconium dichloride, (9-fluorenyl) -methyl-phenyl-polystyrylsilane -cyclopentadienyl zirconium dichloride, dimethyl- (1-indenyl) polystyrylsilane indene 1-zirconium dichloride, (1-indenyl) methyl polystyrylsilane cyclopentadienyl zirconium dichloride, diindenylmethyl polystyrylsilane zirconium dichloride, diphenyl- (9-fluorenyl) polystyryl cyclopentadienyl methane- zirconium dichloride, cyclopentadienyl-diphenyl-polystyrylmethane-cyclopentadienyl-zirconium dichloride, dicyclopentadienyl-methyl-polystyrylmethane-zirconium-dichloride, cyclopentadienyl- (9-fluorenyl) -methyl-polystyryl-dichloromethane-dichloro methyl polystyrylmethane zirconium dichloride, cyclopentadienylmethylphenyl polystyryl methane cyclopentadienyl zirconium dichloride, (1-indenyl) (9-fluorenyl) phenyl polystyryl methane zirconium dichloride, dichloride, (9-Fluorenyl) -methyl-phenyl-polystyryl-methane-cyclopentadienyl-zirconium dichloride, dimethyl- (1-indenyl) -polystyryl-methane-cyclic12 «4« · * ·· lopentadienyl zirconium dichloride, (1-indenyl) methyl polystyryl methane cyclopentadienyl zirconium dichloride and diindenyl m polystyryl ethyl methane zirconium dichloride. Preferred compounds are diphenyl (9-fluoremyl) (polystyrylcyclopentadienyl) silane zirconium dichloride, cyclopentadienyl (9-fluorenyl) methyl polystyrylsilane zirconium dichloride and diphenyl (9- fluorenyl) -polisztiril silane cyclopentadienyl zirconium dichloride.

Polymer-linked metallocenes can be used in combination with suitable cocatalysts to provide catalyst systems for the polymerization of olefins. Suitable cocatalysts include organometallic cocatalysts which have hitherto been developed for transition metal-containing olefin polymerization catalysts. Some typical examples are organometallic compounds of metals of Group IA, LLA and ΓΠΒ of the Periodic Table. Examples of such compounds are organic metal halides, organic metal hydrides and metal hydrides. Examples of such compounds include triethylaluminum, triisobutylaluminum, diethylaluminum chloride and diethylaluminum hydride. Other examples of known cocatalysts include the use of stable non-coordination-bound counter-anions, such as those described in U.S. Patent 5,155,080, such as triphenylcarbenium tetrakis (pentafluorophenyl) boronate. As another example, use is made of a mixture of trimethylaluminum and dimethylfluoroaluminium as described, for example, in Zambelli et al., 1989, Macromolecules, 22, 2186.

Currently, organic aluminoxane cocatalysts are the preferred cocatalysts. Various processes for the preparation of organic aluminoxanes are known. In a known process, water is added to a trialkyl aluminum in a controlled manner. In another known process, a trialkylaluminum is combined with a compound containing adsorbed water or a salt containing crystalline water. Many suitable organic aluminoxanes are commercially available.

Organic aluminoxanes (-O-A1) are generally _X

R ¹ is an oligomeric, linear and / or cyclic hydrocarbylaluminoxane containing a repeating unit of formula wherein each R ¹ is hydrocarbyl, preferably C 1 -C 8 alkyl, X is 2 to 50, preferably 4 to 40 and more preferably 10 -40. Generally, R ¹ is methyl or ethyl. Preferably, at least 30 mol% of the repeating moieties contain a methyl group at R ¹ , more preferably at least 50 and most preferably at least 70 mol% of the repeating moieties contain a methyl group at R ¹ . Generally, organic aluminoxanes are prepared in a mixture of linear and cyclic compounds. Commercially available organic aluminoxanes in hydrocarbon solutions are generally available in aromatic hydrocarbon solutions.

Solid organic aluminoxy products may be prepared by reacting an organic aluminoxane with an oxygen-containing compound such as an organic boroxine, an organic borane, an organic peroxide, an alkylene oxide or an organic carbonate. The use of organic boroxins is preferred.

The amount of organic aluminoxane relative to the polymer-bonded metallocene may vary over a wide range depending upon the particular catalyst selected and the results desired. Generally, the amount of organic aluminoxane is from about 0.5 to about 10,000 moles, preferably from about 10 to about 5,000 moles, and more preferably from about 50 to about 5,000 moles per mole of metal bonded to the polymer. The reaction steps described above for the preparation of the polymer-linked ligand, the polymer-linked metallocene, and the catalyst system are generally carried out in the presence of a solvent or diluent. The solvent or diluent used is, for example, tetrahydrofuran, dichloromethane, toluene, heptane, hexane, cyclohexane, benzene or diethyl ether. Preferably, polymer-linked ligands and polymer-linked metallocenes are prepared using non-coordination solvents such as non-cyclic ethers.

A number of olefinic compounds may be used as monomers in the polymerization process of the present invention. Thus, olefins can be linear, branched, and cyclic aliphatic olefins. Although any known aliphatic olefin may be suitably used with the metallocenes in the process of the present invention, most preferred are olefins having 2 to 18 carbon atoms. Preferably, ethylene and propylene are polymerized. Often a second olefin (comonomer) which

C2-C12, preferably C4-C10, may also be used. Examples of such monomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 2-pentene, 1-hexene, 2-hexene, cyclohexene, 1-heptene and dienes such as butadiene.

The polymerization process according to the invention can be carried out batchwise or continuously. The olefin, the polymer-linked metallocene and the organic aluminoxane cocatalyst can be contacted in any order. Preferably, the polymer-linked metallocene and the organic aluminoxane are contacted prior to contacting the olefin. Generally, a diluent such as isobutane is added to the reactor. The reactor is heated to the desired reaction temperature and an olefin such as ethylene is added and maintained at a partial pressure of about 0.5 to 5.0 MPa for best results. At the end of the desired reaction period, the polymerization reaction is terminated and the unreacted olefin and diluent are expelled from the reactor. The reactor can then be opened and the polymer is obtained as a free flowing white solid which is dried to yield the product polymer.

The conditions of contact between the olefin and the catalyst system may vary widely depending on the olefin used. Generally, the temperature is about 20-300 ° C, preferably 50-110 ° C. The pressure will generally range from about 0.5 to about 5.0 MPa.

The process of the present invention can be used in a gas phase particle forming polymerization process or in a slurry polymerization process. In a particularly preferred particle-forming polymerization process, a continuous loop reactor is used, in which appropriate amounts of diluent, catalyst system and compounds to be polymerized are continuously added in any desired order. Generally, a higher alpha-olefm comonomer and optionally hydrogen are used in the polymerization. Generally, the particle-forming polymerization process is carried out at temperatures of about 50 ° C to about 110 ° C, although higher or lower temperatures may be used. Polyethylenes having different molecular weight distributions can be prepared by varying the amount of hydrogen. The reaction product may be continuously removed from the reactor and the polymer recovered appropriately, generally by evaporation of the diluent and unreacted monomers and drying of the resulting polymer.

The following examples illustrate the present invention without limiting it.

Example 1

Polystyrene was prepared by weighing a solution of 5.00 g of polyvinyl alcohol and 1 liter of water in a 2 L three-necked round-bottom flask equipped with a stirrer, gas inlet and thermometer. Styrene (1.74 mol) was added. The reaction mixture was then added

73.6 ml (0.435 mol) of divinylbenzene (70% by weight in ethyl vinylbenzene) and azobisobutyric acid dinitrile are added and the resulting mixture is stirred. By adjusting the speed of the mixer, the size of the monomer droplets is adjusted. The temperature was raised to 60 ° C. After about 1 hour, particles are visible and the speed of the mixer is doubled to prevent coagulation of the particles. The temperature of the reaction mixture is raised to 90 ° C over a period of 5 hours, and the reaction mixture is maintained at this temperature for 1 hour. The reaction mixture was cooled, filtered and the polymer was washed with water (10 x 21), tetrahydrofuran (THF) (50 mL) and acetone (500 mL). The resulting polystyrene polymer was dried overnight at 80 ° C and then sieved to uniform particle size fractions.

Chloromethylated polystyrene was prepared by reacting 60.00 g of polystyrene with 200 ml of (chloromethyl) methyl ether for 0.5 h at room temperature in a well ventilated extraction chamber. The reaction mixture was cooled to 0 ° C and 12 ml of SnCl ₄ and 50.0 ml of (chloromethyl) methyl ether were added dropwise over 0.5 hour. The reaction mixture was stirred at room temperature for 72 hours and then filtered. The yellow reaction product was treated with 500 mL of dioxane / water (1: 1), 500 mL of dioxane / water / conc. Wash with HCl (2: 2: 1) and 500 mL dioxane. The chloromethylated polystyrene polymer thus obtained was dried for 48 hours at room temperature.

Methyl polystyrylcyclopentadiene is prepared by reacting 20.00 g of chloromethylated polystyrene (24.0 mmol Cl) and 4.15 g (47.11 mmol) of cyclopentadienyl sodium in 100 ml of THF. The reaction mixture was stirred at room temperature for 120 hours. The yellow product was washed with ethanol (5 x 50 mL) and THF (5 x 50 mL). The resulting methyl-polystyryl-cyclopentadiene polymer was dried at room temperature overnight.

Lithium methylated polystyryl cyclopentadiene was prepared by adding 5.90 g of methyl polystyryl cyclopentadiene to 20.0 ml (32.00 mmol) of n-butyl17.

lithium in 50 ml of diethyl ether. The reaction mixture was stirred for 48 hours at room temperature. The supernatant was decanted and the resulting orange lithium methyl polystyryl cyclopentadiene was washed with diethyl ether (3 x 50 mL).

Chlorodiphenyl (9-fluorenyl) silane organic halide is prepared by reacting fluorenyl lithium with dichlorodiphenylsilane. The fluorenyl lithium was prepared by cooling ice-cooling with 25.00 g (150.40 mmol) of fluorene in 94.0 mL (150.40 mmol) of n-butyllithium (1.6 molar hexane solution) in 150 mL of diethyl ether. in ether. The dark red solution was stirred at room temperature overnight. The solvent was removed in vacuo. The resulting yellow solid fluorenyl lithium was added to a solution of dichlorodiphenylsilane (45.0 mL, 216.82 mmol) in pentane (500 mL). The resulting reaction mixture was stirred at room temperature overnight. The solvent was removed in vacuo and the yellow residue was extracted with diethyl ether and filtered through sodium sulfate. The solvent was removed in vacuo and the viscous residue was mixed with 100 mL of pentane. The resulting organic halide compound precipitated chlorodiphenyl (9-fluorenyl) silane as a white solid precipitate. Yield: 80-90%.

A ligand coupled to a diphenyl- (9-fluorenyl) - [(polystyrylmethyl) -cyclopentadienyl] silane polymer is prepared by reacting the chlorodiphenyl- (9-fluorenyl) silane with the lithium methylated polystyrylcyclopentadiene prepared above. Lithium methylated polystyrylcyclopentadienyl was treated with 5 ml of Ν, Ν, Ν ', Ν'-tetramethylethylenediamine and 2.68 g (7.00 mmol) of chlorodiphenyl (9-fluorenyl) silane in 50 ml of diethyl ether. ether. The reaction mixture was stirred at room temperature for 48 hours. The supernatant was decanted and the yellow polymer-linked ligand thus obtained was diphenyl- (918).

Fluorenyl) - [(polystyrylmethyl) cyclopentadienyl] silane was washed with diethyl ether (5 x 50 mL).

Polymer-linked metallocene of diphenyl- (9-fluorenyl) - [(polystyrylmethyl) -cyclopentadienyl] silane-zirconium dichloride is prepared by reacting a lithium polymer-linked ligand with zirconium tetrachloride. The lithiated polymer-linked ligand was prepared by reacting the above diphenyl (9-fluorenyl) - [(polystyrylmethyl) cyclopentadienyl] silane with n-butyllithium (20.0 mL, 32.00 mmol). ml of diethyl ether. The reaction mixture was stirred at room temperature for 48 hours. The supernatant was decanted and the resulting orange polymer was washed with diethyl ether (3 x 50 mL). The lithium polymer-linked ligand thus obtained was reacted with zirconium tetrachloride (1.65 g, 7.08 mmol) in diethyl ether (50 mL). The reaction mixture was stirred overnight at room temperature. The supernatant was decanted and the yellow polymer was washed with diethyl ether (3 x 50 mL). The polymer-linked metallocene thus obtained was dried over diphenyl- (9-fluorenyl) - [(polystyrylmethyl) cyclopentadienyl] silane zirconium dichloride at room temperature overnight.

Example 2

Lithium polystyrene is prepared by reacting brominated polystyrene with n-butyllithium. The brominated polystyrene is prepared by reacting 50.00 g of the above polystyrene (0.4 moles of phenyl) with 6.0 ml of Br ₂ (0.1 mole) and 1.0 g of FeCl _{3 in} 500 ml of chloroform. . The reddish-brown suspension was stirred at room temperature for 48 hours. The polymer was filtered and washed with THF (2 x 100 mL), toluene (6 x 100 mL), acetone (2 x 100 mL), hexane (1 x 100 mL) and diethyl ether (1 x 100 mL). The yellow brominated polystyrene polymer thus obtained was dried at 60 ° C overnight. The brominated polystyrene is then lithiated by reaction of 5.60 g of brominated polystyrene (16.8 mmol Br) with 20.0 mL (32.0 mmol) of n-butyllithium (1.6 molar hexane solution) in 60 mL of toluene. . The reaction mixture was stirred at 60 ° C for 5 hours. During the reaction, the yellow polymer changes to brown. The supernatant was decanted and the lithium polystyrene thus obtained was washed with diethyl ether (5 x 50 ml).

Chlorocyclopentadienyl (9-fluorenyl) methylsilane organic halide is prepared by reacting (9-fluorenyl) methyldichlorosilane with cyclopentadienyl sodium. (9-Fluorenyl) methyl dichlorosilane is prepared by reacting fluorenyl lithium with methyl trichlorosilane. The fluorenyl lithium was prepared by reacting 20 g (120 mmol) of fluorene and 76 mmol of butyllithium (1.6 M in hexane) with 200 mL of diethyl ether. The reaction mixture was stirred at room temperature for 1 hour and then the solvent was removed. The solid fluorenyl lithium thus prepared was added in small portions to a solution of methyl trichlorosilane (36 g, 40 mL, 241 mmol) and pentane (700 mL). The resulting reaction mixture was stirred at room temperature for 1 hour and then filtered through sodium sulfate. The volume of the solution was then reduced to 30% by evaporation and the product crystallized at -30 ° C. The (9-fluorenyl) methyl dichlorosilane thus obtained was a white crystalline powder, 95% yield. Then, (9-fluorenyl) methyldichlorosilane (5 g, 17.9 mmol) was treated with cyclopentadienyl sodium (1.6 g, 18 mmol). The reaction mixture was stirred for 4 hours at room temperature. The reaction mixture was then filtered through sodium sulfate and the solvent removed. Chlorocyclopentadienyl (9-fluorenyl) methylsilane was obtained as a bright yellow solid.

The ligand coupled to the cyclopentadienyl (9-fluorenyl) methyl polystyril silane polymer is prepared by reacting the chlorocyclopentadienyl (9-fluorenyl) methyl silane with lithium polystyrene. As above

The lithium polystyrene prepared is treated with 6.04 g (15.64 mmol) of chlorocyclopentadienyl (9-fluorenyl) methylsilane in 50 ml of diethyl ether. The reaction mixture was stirred at room temperature for 48 hours. The supernatant was decanted and the yellow polymer-linked ligand thus obtained, cyclopentadienyl- (9-fluorenyl) -methyl-polystyrylsilane, was washed with diethyl ether (5 x 50 mL).

The polymer-linked metallocene, cyclopentadienyl- (9-fluorenyl) -methyl-polystyrylsilane-zirconium dichloride, is prepared by reacting the lithium polymer-linked ligand with zirconium tetrachloride. The lithiated polymer-linked ligand is prepared by reacting the above cyclopentadienyl (9-fluorenyl) methyl polystyril silane with n-butyllithium (20 mL, 32.00 mmol) in diethyl ether (50 mL). The reaction mixture was stirred for 48 hours at room temperature. The supernatant was decanted and the orange polymer was washed with diethyl ether (3 x 50 mL). The lithium polymer coupled ligand thus prepared was then reacted with zirconium tetrachloride (3.70 g, 15.87 mmol) in diethyl ether (50 mL). The reaction mixture was stirred overnight at room temperature. The supernatant was decanted and the orange polymer-coupled metallocene, cyclopentadienyl (9-fluorenyl) -methyl-polystyrylsilicon zirconium dichloride thus obtained, was washed with diethyl ether (3 x 50 ml) and dried overnight.

A catalyst system is prepared by activating the polymer-linked metallocene with excess methylaluminoxane (MAO). Using the catalyst system, ethylene was polymerized as follows: Into a 1 L autoclave was added a mixture of 500 mL of hexane and 10 mL of MAO and a predetermined amount of polymer coupled catalyst. The temperature of the autoclave was raised to 60 ° C and maintained at a constant pressure of 0.9 MPa ethylene for 1 hour. By using a polymer 21 coupled catalyst system, no polymer precipitates on the reactor wall during polymerization.

Example 3

Lithium polystyrene was prepared by reacting 1 g of brominated polystyrene prepared as described above in a flask under argon with 10 ml of n-butyllithium (1.6 molar hexane solution) in 30 ml of Tokyo. The reaction mixture was stirred at 60 ° C for 6 hours. The reaction mixture was then washed with diethyl ether (3 x 50 mL).

A ligand coupled to a diphenyl- (9-fluorenyl) -polystyrylsilane polymer was prepared by lithium polystyrene in chloroform (1.53 g, 4 mmol) prepared as described in Example 1 in 50 mL of ether. with silane. The reaction mixture was stirred at room temperature for 14 hours. The reaction mixture turns yellow-green. The solvent was decanted and washed with 2 x 50 mL of food, 50 mL of methanol, and 2 x 50 mL of food.

Polymer-coupled metallocene of diphenyl- (9-fluorenyl) -polystyrylsilane-cyclopentadienyl-dichloride is prepared by reacting the lithiated, polymer-coupled ligand with cyclopentadienyl-zirconium trichloride. The lithiated, polymer-linked ligand is prepared by reacting the diphenyl- (9-fluorenyl) polystyrylsilane prepared as described above with 50 ml of ether in 10 ml of n-butyllithium (1.6 M in hexane). The reaction mixture was stirred at room temperature for 24 hours. The solvent was decanted and the yellow solid residue was washed with 3 x 50 mL of food. Ether (50 mL) and cyclopentadienyl zirconium trichloride (0.79 g, 3 mmol) were then added and the resulting mixture was stirred for 48 hours. The solvent was decanted and the resulting diphenyl- (9-fluorenyl) polystyrylsilane-cyclopentadienyl zirconium dichloride was washed with 3 x 50 mL of food and dried.

An olefin polymerization catalyst system was prepared by reacting 100 mg of diphenyl- (9-fluorenyl) polystyrylsilicyclopentadienyl zirconium dichloride prepared as described above with 5 ml of MAO (30% w / w toluene solution). . The polymerization reactor was charged with 50 mL hexane, 20 mL MAO and ethylene. The catalyst system was introduced into the reactor and the temperature was raised to 60 ° C. The polymerization was continued for 1 hour. 27 g of polyethylene are obtained.

Claims (18)

PATENT CLAIMS A process for preparing a polymer-linked ligand as a metallocene catalyst component, comprising reacting a metallized polystyrene and an organic halide compound, wherein the polystyrene is metallized with an alkali metal and wherein the organic halide compound is represented by the formula XM (R) _m wherein X is a halide, M is Si, C, Ge, Sn, P or N and each R is a hydrocarbon radical independently selected from C 1-36 alkyl, cycloalkyl, aryl or cyclopentadienyl. with the proviso that at least one R is a cyclopentadienyl-type, wherein the cyclopentadienyl-type is cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl and substituted fluorenyl, wherein the substituents are C 1 -C 12 hydrocarbyl, alkoxy groups or halides, and m is 2 or 3. Process according to claim 1, characterized in that the organic halide compound is a chlorosilane, preferably chlorodiphenyl (9-fluorenyl) silane or chlorocyclopentadienyl (9-fluorenyl) methylsilane. Process according to claim 1 or 2, characterized in that the metallized polystyrene is lithium polystyrene or lithium methyl polystyryl cyclopentadiene. 4. The method according to any one of claims 1 to 4, further comprising the steps of: (i) reacting the polymer-linked ligand with an alkali metal compound containing from 1 to 12 carbon atoms to form a metallized polymer-linked ligand, and (ii) reacting the metallized polymer-linked ligand and a metal halide to form a polymer-linked metallocene; wherein the metallized halide compound is represented by the formula ZY ₄ wherein Z is Zr, Hf, Ti or V; and wherein each Y is independently a halide, methyl, or C 5 -C 36 cyclopentadienyl-type, with the proviso that at least three Y substituents are halide. Process according to claim 4, characterized in that the metal halide is zirconium tetrahalide, preferably zirconium tetrachloride or an aryl zirconium trihalide, preferably cyclopentadieml-zirconium trichloride. The process of claim 4, wherein the process further comprises the step of reacting the polymer-linked metallocene with an aluminoxane cocatalyst to form a catalyst system. The process according to claim 6, wherein the aluminoxane cocatalyst is methylaluminoxane and / or the aluminoxane cocatalyst is present in an amount such that from 0.5 to 10,000 mol of aluminum per mole of the metallocene. 8. The product obtained by the process according to any one of claims 1 to 6. 9. QM (R) _m is a polymer-linked ligand, wherein Q is polystyrene, M is Si, C, Ge, Sn, P or N, and each R is independently a hydrocarbon radical, which may be C 1-20 alkyl and cycloalkyl, or C 6-20 aryl, or a cyclopentadienyl type, with 25 that at least one R is a cyclopentadienyl-type and when M is C at least two R is a cyclopentadienyl-type wherein the cyclopentadienyl-type is cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl and substituted fluorenyl, wherein the substituents may be C 1 -C 12 hydrocarbon groups, C 1 -C 12 alkoxy groups or halides, and m is 2 or 3. 10. The polymer-linked ligand of claim 9, wherein M is Si, and the ligand is preferably (9-fluorenyl) diphenyl- (polystyryl-cyclopentadienyl) -silane, (9-fluorenyl) -cyclopentadienyl-methyl-polystyryl-. silane, (9-fluorenyl) diphenyl polystyryl silane, (9-fluorenyl) cyclopentadienylmethyl (polystyrylmethyl) silane, or (9-fluorenyl) diphenyl (polystyrylmethyl) silane. 11. Metallocenes linked to a polymer of the formula QM (R) _m ZY _n , wherein: Q is polystyrene, M is Si, C, Ge, Sn, P or N, and each R is independently a hydrocarbon radical, which may be C 1-20 alkyl and cycloalkyl, or C 6-20 aryl, or a cyclopentadienyl type, with the proviso that that at least one R is a cyclopentadienyl-type and when M is C, at least two R is a cyclopentadienyl-type, wherein the cyclopentadienyl-type is cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl - and may be substituted fluorenyl, wherein the substituents may be C 1 -C 12 carbon, hydrogen, C 1 -C 12 alkoxy or halide, and m is 2 or 3, Z is Zr, Hf, Ti or V; and wherein each Y is independently a halide, methyl, hydrogen, or C 5 -C 36 cyclopentadienyl-type, and n is 2 or 3. A polymer-linked metallocene according to claim 11, wherein Z is Zr, and wherein the metallocene is preferably (9-fluorenyl) diphenyl (polystyrylcyclopentadienyl) silane zirconium dichloride, (9-fluorenyl) cyclopentadienyl- methyl-polystyrylsilane-zirconium dichloride, (9-fluorenyl) -diphenyl-polystyryl-silicon-cyclopentadienyl-zirconium-dichloride, (9-fluorenyl) -cyclopentadienyl-methyl-polystyrylmethyl-silicon-zirconium dichloride or (9) fluorenyl) -difenil- (methyl polystyryl) silane cyclopentadienyl zirconium dichloride. 13. A polymerization catalyst system, characterized in that it comprises a polymer-linked metallocene and an aluminoxane cocatalyst, wherein the polymer-linked metallocene is represented by the formula QM (R) _m ZY _n , wherein Q is polystyrene, M is Si, C, Ge, Sn, P or N, and each R is independently a hydrocarbon radical, which may be C 1-20 alkyl and cycloalkyl, or C 6-20 aryl, or a cyclopentadienyl type, with the proviso that that at least one R is a cyclopentadienyl-type and when M is C, at least two R is a cyclopentadienyl-type, wherein the cyclopentadienyl-type is cyclopentadienyl, substituted cyclopentadienyl, enyl, indenyl, substituted indenyl, fluorenyl and substituted fluorenyl, wherein the substituents may be C 1 -C 12 hydrocarbon groups, C 1 -C 12 alkoxy groups or halides, and m is 2 or 3, Z is Zr, Hf, Ti or V; and wherein each Y is independently a halide, methyl, hydrogen, or C 5 -C 36 cyclopentadienyl-type, and n is 2 or 3; and wherein the organic aluminoxanes (-O-A1) are _X R ¹ is a repeating unit of the formula wherein each R ¹ is C 1 -C 8 hydrocarbyl and x is 2 to 50. 14. A polymerization process, wherein the at least one olefin is contacted under polymerization conditions with the catalyst system of claim 13. Process according to claim 14, characterized in that the polymerization is carried out at a temperature of from 20 to 200 ° C, preferably from 50 to 110 ° C. The process of claim 15, wherein the polymerization is performed under particle-forming conditions. 17. The process of claim 14, wherein the at least one olefin is ethylene. 18. A polymerization catalyst system comprising essentially a polymer-linked metallocene and an aluminoxane cocatalyst, wherein the polymer-linked metallocene is represented by the formula QM (R) _m ZY _n , wherein: Q is polystyrene, M is Si, C, Ge, Sn, P or N, and each R is a hydrocarbon radical independently selected from C 1-20 alkyl and cycloalkyl, or C 6-20 aryl, or a cyclopentadienyl type, with the proviso that that at least one R is a cyclopentadienyl-type and when M is C, at least two R is a cyclopentadienyl-type, wherein the cyclopentadienyl-type is cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl - and may be substituted fluorenyl wherein the substituents may be C 1 -C 12 hydrocarbon groups, C 1 -C 12 alkoxy groups or halides and m is 2 or 3, Z is Zr, Hf, Ti or V; and wherein each Y is independently a halide or a C 5 -C 36 cyclopentadienyl-type group, and n is 2 or 3; and wherein the organic aluminoxanes comprise a repeating unit of the formula (-O-A1) _X , wherein each R ¹ is C 1 -C 8 hydrocarbyl and x is 2 to 50.